Hartree potential dependent exchange functional

Journal Article · Sun Aug 28 04:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4961300· OSTI ID:22678893

Constantin, Lucian A. ^[1]; Fabiano, Eduardo; Della Sala, Fabio ^[1]

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1. Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia, via Barsanti, I-73010 Arnesano (Italy)

We introduce a novel non-local ingredient for the construction of exchange density functionals: the reduced Hartree parameter, which is invariant under the uniform scaling of the density and represents the exact exchange enhancement factor for one- and two-electron systems. The reduced Hartree parameter is used together with the conventional meta-generalized gradient approximation (meta-GGA) semilocal ingredients (i.e., the electron density, its gradient, and the kinetic energy density) to construct a new generation exchange functional, termed u-meta-GGA. This u-meta-GGA functional is exact for the exchange of any one- and two-electron systems, is size-consistent and non-empirical, satisfies the uniform density scaling relation, and recovers the modified gradient expansion derived from the semiclassical atom theory. For atoms, ions, jellium spheres, and molecules, it shows a good accuracy, being often better than meta-GGA exchange functionals. Our construction validates the use of the reduced Hartree ingredient in exchange-correlation functional development, opening the way to an additional rung in the Jacob’s ladder classification of non-empirical density functionals.

• OSTI ID: 22678893
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 145; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CONSTRUCTION
DENSITY FUNCTIONAL METHOD
ELECTRON DENSITY
ENERGY DENSITY
IONS
KINETIC ENERGY
SEMICLASSICAL APPROXIMATION
SYNTHESIS